Graphene-based antiviral polymer

ABSTRACT

An antiviral material is provided. The antiviral material includes a polymeric matrix and graphene particles dispersed in the polymeric matrix at a concentration of greater than or equal to about 0.05 wt. % to less than or equal to about 10 wt. % based on the total weight of the antiviral material, wherein the antiviral material exhibits antiviral activity. Methods of making the antiviral material and uses of the antiviral material are also provided.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.63/080,417, filed on Sep. 18, 2020, which is incorporated by referenceherein.

FIELD

The present disclosure relates to polymeric materials includingantimicrobial particles that are suitable for high touch surfaces.

BACKGROUND AND SUMMARY

The present application generally pertains to antimicrobial materialsand, more particularly, to antiviral materials that inactivate ordestroy coronaviruses.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) epidemichas changed the way hygiene is managed and maintained in public andother shared spaces. SARS-CoV-2, which causes coronavirus disease 2019(COVID-19), and other deadly microbes can transmit through directperson-to person contact, from the uptake of contaminated airbornedroplets, or even from contact with contaminated surfaces such asvehicle interiors. The use of antiviral materials is an effective way toinactivate viral particles in the environment, which prevents viraltransmission, thus lowering the risk of infection.

Polymers are ubiquitous materials found on many public and sharedspaces. Polymers have many applications in disposable cutleries, cars,aircrafts, cruise ships, and stadiums. A shared economy has led to agrowth of multiple users using the same vehicle at different times.Rental cars and other shared vehicles are affected by SARS-Covid-2, asthe virus can be easily transmitted by coming in contact with it.Therefore, antiviral polymeric materials that can significantly diminishthe amount of virus present on surfaces over time are desired.

In accordance with the present invention, an antimicrobial material isprovided. The antimicrobial material has antiviral activity and includesa polymeric matrix and graphene particles dispersed in the polymericmatrix at a concentration of greater than or equal to about 0.05 wt. %to less than or equal to about 10 wt. % based on the total weight of theantiviral material. In a further aspect, the antimicrobial materialincludes metal oxide particles dispersed in the polymer matrix, themetal oxide particles including at least one of cuprous oxide (Cu₂O)particles or zinc oxide (ZnO) particles. In another aspect, theantiviral material is flexible and the polymeric matrix includes apolymer including flexible and/or rigid polyvinyl chloride (PVC), athermoplastic elastomer (TPE), or a combination thereof, wherein the TPEincludes a thermoplastic polyurethane (TPU), a thermoplastic polyolefin(TPO), thermoplastic vulcanizates (TPV), or combinations thereof. In yetanother aspect, the antiviral material is rigid and the polymeric matrixincludes a polymer including polypropylene (PP), acrylonitrile butadienestyrene (ABS), polycarbonate (PC), PC/ABS, PC/PP, a thermoplasticelastomer (TPE), or combinations thereof.

The antimicrobial material is useful as a surface of an automotivevehicle selected from the group consisting of an A-pillar, a B-pillar, aC-pillar, an instrument panel, a steering wheel skin, an airbag cover, adoor trim panel, a center console, a knee bolster, a seat mechanismcover, and a sun visor. The antimicrobial material is also useful innon-automotive vehicle applications, such as for a seat, a bench, anexercise bench, a bicycle handle, a motorcycle handle, a vital signsmonitor, hospital equipment, a door hand panel, a door foot panel, adoor knob or handle, a door opening actuator, an airplane cabin wall, anairplane storage bin, an airplane seat, an airplane tray table, a cruiseship surface, a counter top, a flooring, a matt, an electrical device, aski lift chair or rail, or a sports locker.

The present antimicrobial material is advantageous over conventionalpolymeric materials. For example, it is can be cast or molded intoflexible or rigid articles that can be used wherever conventionalpolymeric materials are used. Because the antimicrobial material hasantiviral activity, it is especially useful for surfaces that are oftentouched by human subjects. Accordingly, the antimicrobial material isuseful for destroying viruses, including coronaviruses, and decreasingrisks of viral infection when contacting polymeric surfaces that arecommonly encountered.

DRAWINGS

The drawings described herein are for illustrative purposes only ofselected embodiments and not all possible implementations, and are notintended to limit the scope of the present disclosure.

FIG. 1 is a perspective view showing an interior trim panel havingantimicrobial surfaces in accordance with various aspects of the currenttechnology.

FIG. 2 is a cross-sectional view, taken along line 2-2 of FIG. 1 ,showing the interior trim panel.

FIG. 3 is a perspective view showing an A-pillar, a handle, and a doorskin having surfaces including antimicrobial materials in accordancewith various aspects of the current technology.

FIG. 4 is a cross-sectional view, taken along line 4-4 of FIG. 3 ,showing the A-pillar and the handle.

FIG. 5 is a cross-sectional view, taken along line 5-5 of FIG. 3 ,showing the door skin.

FIG. 6 is a perspective view showing a chair having surfaces includingan antimicrobial material in accordance with various aspects of thecurrent technology.

FIG. 7 is a cross-sectional view, taken along line 7-7 of FIG. 6 ,showing a backrest portion of the chair.

FIG. 8 is a cross-sectional view, taken along line 8-8 of FIG. 6 ,showing a sitting surface of the chair.

FIG. 9 is a perspective view showing an exercise bench having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 10 is a cross-sectional view, taken along line 10-10 of FIG. 9 ,showing an outer surface of the exercise bench.

FIG. 11 is a perspective view showing a public transit seat having asurface including an antimicrobial material in accordance with variousaspects of the current technology.

FIG. 12 is a cross-sectional view, taken along line 12-12 of FIG. 11 ,showing the seat.

FIG. 13 is a perspective view showing a bicycle handle having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 14 is a cross-sectional view, taken along line 14-14 of FIG. 13 ,showing the handle.

FIG. 15 is a perspective view showing a vital signs monitor havingexposed components including an antimicrobial material in accordancewith various aspects of the current technology.

FIG. 16 is a perspective view showing a door having surfaces and ahandle including antimicrobial materials in accordance with variousaspects of the current technology.

FIG. 17 is a cross-sectional view, taken along line 17-17 of FIG. 16 ,showing a hand plate on the door.

FIG. 18 is a perspective view showing an airplane cabin having surfacesincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 19 is a cross-sectional view, taken along line 19-19 of FIG. 18 ,showing a sitting portion of a seat located within the airplane cabin.

FIG. 20 is a cross-sectional view, taken along line 20-20 of FIG. 18 ,showing an armrest of a seat located within the airplane cabin.

FIG. 21 is a perspective view showing a countertop having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 22 is a cross-sectional view, taken along line 22-22 of FIG. 21 ,showing the countertop.

FIG. 23 is a perspective view showing flooring having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 24 is a cross-sectional view, taken along line 24-24 of FIG. 23 ,showing the countertop.

FIG. 25 is a perspective view showing a matt composed of anantimicrobial material in accordance with various aspects of the currenttechnology.

FIG. 26 is a cross-sectional view, taken along line 26-26 of FIG. 25 ,showing the matt.

FIG. 27 is a perspective view showing a computer having surfacesincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 28 is a cross-sectional view, taken along line 28-28 of FIG. 27 ,showing a key of the computer.

FIG. 29 is a perspective view showing a credit card machine havingsurfaces including an antimicrobial material in accordance with variousaspects of the current technology.

FIG. 30 is a cross-sectional view, taken along line 30-30 of FIG. 29 ,showing the credit card machine.

FIG. 31 is a perspective view showing a ski lift having surfacesincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 32 is a cross-sectional view, taken along line 32-32 of FIG. 31 ,showing a seating surface of the ski lift.

FIG. 33A is a cross-sectional view, taken along line 33-33 of FIG. 31 ,showing the seating surface.

FIG. 33B is a perspective view showing a sports locker having surfacesincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 34 is a cross-sectional view, taken along line 34-34 of FIG. 33 ,showing a wall of the sports locker.

FIG. 35 is a cross-sectional view, taken along line 35-35 of FIG. 33 ,showing drawers of the sports locker.

FIG. 36 is a perspective view showing a rigid pipe having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 37 is a perspective view showing a flexible pipe having a surfaceincluding an antimicrobial material in accordance with various aspectsof the current technology.

FIG. 38 is a perspective view showing a first antimicrobial material inaccordance with various aspects of the current technology.

FIG. 39 is a perspective view showing a second antimicrobial material inaccordance with various aspects of the current technology.

FIG. 40 is a perspective view showing a third antimicrobial material inaccordance with various aspects of the current technology.

FIG. 41 is a perspective view showing an antimicrobial material disposedon at least one sublayer in accordance with various aspects of thecurrent technology.

FIG. 42 is a diagrammatic flow chart showing a method for making anantimicrobial material in accordance with various aspects of the currenttechnology.

Corresponding reference numerals indicate corresponding parts throughoutthe several views of the drawings.

DETAILED DESCRIPTION

Example embodiments will now be described more fully with reference tothe accompanying drawings.

The current technology provides antimicrobial polymers used forproducing automotive interior products, synthetic leather, gymequipment, flooring, wallets, medical instruments or medical plastics,electronics (e.g., housings, keyboards, laptops, and the like), publictransit surfaces (e.g., automotive vehicle interior surfaces, waitingbenches, handrails, and the like), cruise ship interior surfaces, sportsequipment, and plastic door handles/pads. Automotive interior productsinclude soft skins, seating materials, class-A hard trim components,such as map-pocket, A-pillars, B-pillars, C-pillars, consoles, doors,and instrument panels. All of the above applications are exemplary andnon-limiting as it is understood that the current technology isapplicable to all plastic surfaces that are configured to be touched byhuman subjects.

The current technology also provides graphene-based antiviral polymersfor automotive vehicle and aircraft interior parts and other high touchsurfaces. As non-limiting examples, the interior part can be an interiortrim panel, an automotive vehicle instrument panel, an airbag cover, adoor trim panel, a center console, a knee bolster, a seat mechanismcover, a sun visor, a pillar cover, or the like. Other high touchsurfaces include synthetic leather, flooring, gym equipment, wallets,medical instruments or medical plastics, hospitals, electronics (e.g.,keyboards, laptops credit card machines, and the like), public transitapplications, including public transport vehicle interiors and subway ortrain station benches, handrails, and the like, cruise ship interiors,sports equipment, gas pumps (including housing, key pads, and pumphandles), and polymeric door handles and pads.

In certain aspects, the current technology provides graphene- orgraphene-metal oxide complex-infused rigid and/or flexible PVC, TPU, TPOand injection grade PP, TPE, TPO, ABS, PC/ABS, and PC/PVC. Similarpolymers, such as PE, nylon, and the like, are also contemplated. Asused herein, the term “rigid” means that the “rigid” materials issubstantially inflexible. In other words, the rigid materials may bebendable to a slight extent, but are at risk of cracking or breakingafter a bending threshold is reached, such as may be exhibited by anautomotive vehicle interior panel. On the other hand, “flexible”materials can be heavily bent or folded without cracking or breaking,such as may be exhibited by a synthetic leather.

Articles with Antimicrobial Surfaces

An interior trim panel for a wheeled automotive land vehicle is shown inFIGS. 1 and 2 . The interior trim panel is preferably an instrumentpanel 10 but may alternately include a center console 12, a separateairbag cover, a door trim panel, center console, a knee bolster, a seatmechanism cover, a sun visor, a pillar cover, or the like. Instrumentpanel 10 includes an outer skin 14, a middle pliable foam layer 16 andan inner rigid substrate 18. Also, a steering wheel 29 extends from theinstrument panel 10.

A section of skin 14 acts as an integral airbag door 20 behind which isan airbag assembly 22 including a chute 24. Airbag door 20 hinges orpivots about upper and lower flexure lines adjacent generallyhorizontally elongated substrate edges 26 when an expanding airbagbursts tear seams 28 in skin 14. A “seamless” or hidden style of skin 14is preferred whereby tear seams 28 are on the backside surface thereofand are not visible to the vehicle occupant or user. Tear seams 28preferably have an H-shape, although other configurations such asU-shapes, and X-shapes can be employed. Each of the above components ofthe instrument panel 10 can comprise an antimicrobial material of thecurrent technology. For example, each of the instrument panel 10, centerconsole 12, airbag cover, door trim panel, center console, knee bolster,seat mechanism cover, pillar cover, a steering wheel, and air bag door20 can include an outer skin including a flexible antimicrobial materialof the current technology or be composed of a rigid antimicrobialmaterial of the current technology.

An A-pillar trim panel 30 including a handle 32 and an interior doortrim panel 34 are shown in FIGS. 3-4 . The A-pillar trim panel 30 andthe handle 32 include an outer surface including an antimicrobialmaterial of the current technology. At last one flexible fastener isprovided on a back side of the A-pillar trim panel 30 to removablyretain the A-pillar trim panel 30 to an underlying sheet metal A-pillarstructure. Although not shown in FIGS. 3-4 , it is understood thatB-pillar trim panels and C-pillar trim panels can have the sameconfiguration as the A-pillar trim panel 30.

The door trim panel 34 includes a flexible outer skin 36, anintermediate compressible foam layer 38 and an inner rigid substrate 40.The inner rigid substrate 40 is removably secured to a sheet metal doorstructural panel 42 by fasteners. Furthermore, the flexible outer skin36 includes an antimicrobial material of the current technology and theinner rigid substrate 40 is molded from a polymer or from fiber-basedcomposites.

As can be observed in FIGS. 6-8 , a chair 50 has surfaces including theantimicrobial material of the current technology. The chair 50 includesa sitting surface 52 and a backrest 54. The sitting surface 52 includesan outer antimicrobial surface 56 including an antimicrobial material ofthe current technology. The outer antimicrobial surface 56 is disposedon a compressible foam layer 58 and the compressible foam layer 58 isdisposed on an inner rigid substrate 60. The backrest 54 may onlyinclude the antimicrobial material, but can alternatively include thesame components of the sitting surface 52.

With reference to FIGS. 9-10 , an exercise or workout bench 70 includesa surface 72 configured to be sat on or laid on. The surface 72 includesan outer antimicrobial surface 74 including an antimicrobial material ofthe current technology. The outer antimicrobial surface 74 is disposedon a compressible foam layer 76, which is disposed on an inner rigidsubstrate 78.

FIGS. 11-12 show a public transit seat 80 having a first exposed surface82 and a second exposed surface 84 disposed on the first exposed surface82. Whereas the first exposed surface 82 is rigid, the second exposedsurface can be rigid or soft and flexible. At least one of the exposedsurfaces 82, 84 includes an antimicrobial material of the currenttechnology. FIG. 11 also shows a handrail 86 located adjacent to theseat 80. An exterior surface of the handrail 86 can also include anantimicrobial material of the current technology.

Referring to FIGS. 13-14 , a bicycle handle 90 has an outer surface 92including an antimicrobial material of the current technology. The outersurface 92 is disposed on and about a rigid polymeric, metal, or steelsubstrate 94. A motorcycle handle can have the same or substantiallysimilar configuration.

Electronic devices including an outer, protective housing, internalelectrical circuits, a power supply, and human-contactable surfaces,such as buttons, knobs, and display screens, employ an antimicrobialmaterial according to the current technology on an outside surfacethereof. One example of such an electronic device is a vital signsmonitor 100 as provided in FIG. 15 . The vital signs monitor 100includes a housing 102, buttons 104, a knob 106, and a screen 108. Atleast one of the housing 102, buttons 104, knob 106, or screen 108includes an antimicrobial material of the current technology.

With reference to FIGS. 16-17 , a door 110 includes a handle 112, a handplate 114, and a kick plate 116. The door 110 is a residential,commercial, office, or manufacturing plant door coupled to a stationarydoorjamb. Although the door 110 is shown with the handle 112, the handle112 can alternatively be a knob. At least one of the handle 112, handplate 114, and kick plate 116 includes an antimicrobial material of thecurrent technology. Adjacent to the door is a button 120 for opening thedoor 110. The button is part of an electronic device internallyincluding an electrical switch and circuits. An exterior surface of thebutton 120 includes the antimicrobial material.

FIGS. 18-20 show aspects of an airplane cabin 130. The airplane cabinincludes a storage bin 132, a wall 134, and a seat 136. The storage bin132 and the wall 134 including an antimicrobial material of the currenttechnology. The seat 136 includes a sitting portion 138, a backrest 140,and armrests 142. The sitting portion 138 includes an outer skin 144including an antimicrobial material of the current technology, which isdisposed on a compressible foam substrate 146. The backrest 140 can havethe same or substantially similar configuration. The armrests 142comprise a second outer skin 148 disposed on a rigid metal or steelsubstrate 150. Although not shown, an airplane tray table can also havea surface including an antimicrobial material of the current technology.

As shown in FIGS. 21-22 , a countertop 160 has an outer surface 162including an antimicrobial material of the current technology. The outersurface 162 is disposed on a rigid substrate 164 including a rigidpolymer, a metal, steel, or wood. Shelves, drawers, or the like mayoptionally be located in a counter supporting the rigid substrate 164 ofthe countertop 160.

FIGS. 23-24 depict a flooring 170 having an outer wear layer 172including an antimicrobial material of the current technology. Althoughvarious architectures as possible, in the flooring 170, the wear layeris disposed on a paper or print layer 174, which is disposed on a firstrigid under layer 176, such as a high density fiberboard, which isdisposed on a second under layer 178, such a foam under layer.

FIGS. 25-26 provide an illustration of a matt 180. The matt 180 can be,for example, an exercise matt or a yoga matt that is flexible andportable (for hand carrying by a user). The matt 180 includes anantimicrobial material of the current technology.

Another exemplary electrical device is shown in FIGS. 27-28 , as acomputer 190, such as a notebook or laptop. The computer 190 includes ahousing 192 including an antimicrobial material of the currenttechnology. The computer 190 also includes a plurality of keys 194,wherein each key 194 of the plurality includes an outer surface layer196 including an antimicrobial material of the current technology. Theouter surface layer 196 is disposed on a rigid substrate 198.

A further exemplary electrical device is shown with reference to FIGS.29-30 , as a credit card machine 200, which may be a credit card reader.The credit card machine 200 includes a housing 202 and a plurality ofbuttons 204. The housing and the buttons 204 comprise an antimicrobialmaterial of the current technology.

FIGS. 31-32 show a ski lift 210 including handrails 212. The handrailsincluding an outer surface layer 214 disposed on and about a rigid metalor steel substrate 216. The outer surface layer 214 includes anantimicrobial material of the current technology. The ski lift 210 alsoincludes a seat 218 including a sitting portion 220 and a backrest 222.The sitting portion 220 and the backrest comprise an antimicrobialmaterial of the current technology.

As can be seen in FIGS. 33-35 , a sports locker 230 includes walls 232,drawers 234, and a shelf 236. The walls 232 have an outer layer 238including an antimicrobial material of the current technology, which isdisposed on a rigid substrate 240. The shelf 236 also has an outersurface including an antimicrobial material of the current technology.The drawers 234 have an outer drawer layer 242 including anantimicrobial material of the current technology, wherein the outerdrawer layer 242 is disposed on a rigid drawer substrate 244.

FIG. 36 shows a rigid pipe 250 including a rigid body or outer surface252 including an antimicrobial material of the current technology,wherein the rigid body or outer surface 252 defines a hollow interiorcore 254. As a non-limiting example, the rigid body or outer surface 252can include rigid PVC. FIG. 37 shows a flexible pipe 260 including aflexible body or outer surface 262 including an antimicrobial materialof the current technology, wherein the flexible body or outer surface262 defines a hollow interior core 264. As a non-limiting example, theflexible body or outer surface 262 can include flexible PVC. The pipes250, 260 exhibit antimicrobial activity, including antiviral activity,and are useful at least in plumbing applications as fresh water pipesand sewage pipes. For example, the rigid body or outer surface 252.Exemplary materials and methods serving as a basis for making the pipes250, 260 can be found in U.S. Pat. No. 8,178,640, which is incorporatedherein by reference in its entirety. For example, the PVC materials inU.S. Pat. No. 8,178,640 can be modified in accordance with the currenttechnology in order to exhibit antimicrobial activity.

Antimicrobial Materials

With reference to FIG. 38 , the current technology provides anantimicrobial material 300. As used herein, the term “antimicrobial”provides that the antimicrobial material 300 has antiviral properties,i.e., the antimicrobial material 300 is an antiviral material, and insome aspects, also has antibacterial properties, i.e., the antimicrobialmaterial 300 can be an antiviral and antibacterial material, and/orantifungal properties, i.e., the antimicrobial material 300 can be anantiviral and antibacterial and/or antifungal material. As such, when avirus contacts the antimicrobial material 300, the virus is disabled,inactivated, destroyed, or “killed” such that the virus is no longercapable of infecting a subject. Similarly, when the antimicrobialmaterial has antibacterial properties, when a bacterium contacts theantimicrobial material 300, the bacterium is killed. The term“antiviral” provides that the antiviral material disables, inactivates,destroys, or “kills” at least SARS-CoV-2, and in some aspects, alsokills other viruses, including other coronaviruses. The antimicrobialmaterial 300 has antiviral activity due to its ability, for example, todisrupt virus host cell recognition by denaturing protein structures onviral surfaces, leading to the inactivation of viruses regardless of thepresence of a viral envelope. The antimicrobial material 300 disables,inactivates, destroys, or “kills” greater than or equal to about 90%,greater than or equal to about 95%, greater than or equal to about 98%,greater than or equal to about 99%, such as about 90%, about 91%, about92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%,about 99%, or about 99.9%, of SARS-CoV-2 viral particles or plaqueforming units (PFUs) in less than or equal to about 4 hours, less thanor equal to about 3 hours, less than or equal to about 2 hours, lessthan or equal to about 1 hours, less than or equal to about 45 minutes,less than or equal to about 30 minutes, or less than or equal to about15 minutes.

The antimicrobial material 300 includes a polymeric matrix 312 andgraphene particles 314 disposed and/or embedded in the polymeric matrix312, including at an exposed surface 315. As used herein, a “polymericmatrix” is a bulk polymer-based composition or material. Accordingly,the polymeric matrix 312 comprises at least one solidified or curedpolymer that embeds antimicrobial particles, such as the grapheneparticles 314. Depending on a predetermined application, theantimicrobial material 300 can be flexible and soft or relatively rigid.The hardness, rigidness, and flexibility of the antimicrobial material300 is provided by the polymer matrix 312, which includes a polymer. Forexample, for applications requiring soft and flexible materials, such asfor a synthetic leather or skin, as non-limiting examples, the polymerof the polymer matrix 312 includes polyvinyl chloride (PVC), athermoplastic elastomer (TPE), or a combination thereof. The TPEincludes a thermoplastic polyurethane (TPU), a thermoplastic polyolefin(TPO), thermoplastic vulcanizates (TPV), or combinations thereof.Non-limiting examples of TPUs include reaction products of aromatic oraliphatic isocyanates with a polyether or polyester polyol, such asTEXIN® 3042 TPU (Covestro). Non-limiting examples of TPOs include olefinblock copolymers (OBCs), INFUSE™ olefin block copolymer resins (Dow),ENGAGE™ polyolefin elastomer resins (Dow),styrene-ethylene-butylene-styrene (SEBS) polymer, such as KRATON™ SEBSpolymer (Kraton), and the like. For applications requiring rigidmaterials, such as for a pillars, and panels, as non-limiting examples,the polymer of the polymer matrix 312 includes polypropylene (PP),acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC/ABS,PC/PP, a TPE, or combinations thereof. Non-limiting examples of TPUsinclude aliphatic and aromatic TPUs, such as TEXIN® TPUs (Covestro).Non-limiting examples of hard TPEs include OBCs, INFUSE™ olefin blockcopolymer resins (Dow), ENGAGE™ polyolefin elastomer resins (Dow),styrene-ethylene-butylene-styrene (SEBS) polymer, such as KRATON™ SEBSpolymer (Kraton), and the like. Additional applications for soft andhard antimicrobial materials are provided below.

Polymers include poly vinyl chloride (PVC), styrene acrylo nitrile(SAN), poly styrene (PS), poly methyl methacrylate (PMMA), ABS, styrenemaleic anhydride (SMA), polyphenylene oxide (PPO), ply carbonate (PC),poly phthalate carbonate (PPC) poly tetrafluoro ethylene (PTFE),polyacrylate (PAR) ply ether sulfone (PES), poly ether imide (PEI), polyphenyl sulfone (PPSU), thermoplastic polyimide (TPI), poly amide imide(PAI), high density polyethylene (HDPE), low density poly ethylene(LDPE), poly propylene (PP), ultra high molecular weight poly ethylene(UHMWPE), poly oxy methylene (POM), poly amide (PA), poly butyleneterephthalate (PBT), poly ethylene terephthalate (PET), poly amide-4,6(PA-4,6), poly phthal amide (PPA), poly phenylene sulfide (PPS), liquidcrystal polymers (OCP), poly vinyl diene fluoride (PVDF), fluoropolymers (FP), poly ether ether ketone (PEEK), and combinations thereof,as non-limiting examples.

Soft Skins for automotive interiors are conventionally used on consoles,armrests, door-uppers, and instrument panels applications. Automotivevehicle soft skins are made from a variety of polymeric materialsincluding flexible PVC, TPU, TPO, and TPEs. These skins can be producedby methods such as slush rotational molding, injection molding,thermoforming, and from cut and sew applications. Accordingly, thepolymer of the polymer matrix 312 can include PVC, TPU, TPO, and TPEscan be used as a polymer of the polymer matrix 312.

Automotive vehicle interior Class-A hard trim materials areconventionally made from a variety of polymeric materials including PP,TPO, TPE, and glass/talc/mineral-filled PP/TPO/TPE, which can comprisethe polymer of the polymer matrix 312. These Class A hard trim materialscan be made by methods such as injection molding and compression moldingusing polymers including PP, TPO, TPE, and glass/talc/mineral-filledPP/TPO/TPE for the polymer matrix 312.

Synthetic leather is made up of flexible PVC, TPU, TPV, and TPO and isconventionally produced in a calendaring process via melt extrusion andused as an alternative to animal leather for decorating/A-surfacematerial on automotive interiors and in furnishings. Accordingly, theflexible PVC, TPU, TPV, and TPO can be used as a polymer of the polymermatrix 312.

Interior automotive polymers, components, panels, trim, and skins aredescribed in U.S. Pat. Nos. 10,358,159; 10,328,881; 10,232,755;10,093,268; 9,713,972; 9,539,745; 9,440,385; 5,824,738; U.S. PatentPublication No. 2020/0139814; U.S. Patent Publication No. 2019/0344689;U.S. Patent Publication No. 2018/0044536; U.S. Patent Publication No.2017/0100992; and U.S. Patent Publication No. 2015/0360597; all of whichare incorporated herein by reference in their entirety.

Other high touch surfaces that can benefit from the current technologyinclude synthetic leather, gym equipment, flooring, wallets, medicalinstruments or medical plastics, electronics (e.g., housings, keyboards,laptops, credit card machines, and the like), public transit surfaces(e.g., automotive vehicle interior surfaces, waiting benches, handrails,and the like), cruise ship interior surfaces, sports equipment, andplastic door handles/pads. The polymer matrix 312 of these high touchsurfaces can comprise PP, TPE, TPO, TPV, ABS, PC/ABS, PC/PVC, andcombinations thereof, as non-limiting examples. These products areproduced using rotational molding, injection molding, calendaring,extruding, thermoforming, cut and sew applications, and combinationsthereof.

The graphene particles 314 are antimicrobial particles or flakesincluding graphene or a graphene derivative, such as graphene oxide as anon-limiting example, that provide at least the antiviral activity. Thegraphene particles 314 have greater than or equal to 1 to less than orequal to 10 layers or greater than or equal to 6 to less than or equalto 10 layers, wherein each layer includes carbon atoms arranged in atwo-dimensional honeycomb-shaped lattice. In various aspects, thegraphene particles 314 have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 of thelayers. The graphene particles 314 have a diameter of greater than orequal to about 750 nm to less than or equal to about 250 μm, greaterthan or equal to about 1 μm to less than or equal to about 100 μm, orgreater than or equal to about 1 μm to less than or equal to about 50μm.

Without being bound by theory, the antimicrobial properties of graphene,and graphene-derivatives (e.g., graphene oxide), are attributed to theirelectron movement towards microbes. This migration causes cytoplasmicefflux, decreases metabolism, affects lipid membrane, induces oxidativestress, produces reactive oxygen species (ROS), loss of glutathione, andfinally causes microbial death. As non-limiting examples, graphene canbe used to kill different coronaviruses, including SARS-CoV strains.

In some aspects, the antimicrobial material 300 includes an additionalantimicrobial agent. FIGS. 39 and 40 shows antimicrobial materials 300a, 300 b including the polymeric matrix 312 and the graphene particles314. However, the antimicrobial materials 300 a, 300 b further includesmetal oxide particles 316, wherein the metal oxide particles 316 alsoprovide at least antiviral activity against as defined above in regardto the graphene particles 314. The metal oxide particles 316 includescuprous oxide (Cu₂O) particles, zinc oxide (ZnO) particles, silver oxide(Ag₂O), or combinations thereof. These metal oxide particles releaseantimicrobial ions, such as Cu¹⁺, Ag¹⁺ and/or Zn²⁺, and are used toprepare antimicrobial surfaces. Graphene and/or graphene oxide canpromote antimicrobial activities of these ions further and improve theeffectiveness. The metal oxide particles have a diameter of greater thanor equal to about 100 nm to less than or equal to about 100 μm, greaterthan or equal to about 200 nm to less than or equal to about 10 μm,greater than or equal to about 250 nm to less than or equal to about 5μm, or greater than or equal to about 250 nm to less than or equal toabout 1.8 μm.

As shown in FIG. 39 , the graphene particles 314 and the metal oxideparticles 316 are individually uniformly dispersed throughout thepolymeric matrix 312 in the antimicrobial material 300 a. By“individually uniformly dispersed,” it is meant that the grapheneparticles 314 and the metal oxide particles 316 are blended within thepolymer matrix 312 without respect to each other. Inasmuch as somegraphene particles 314 and metal oxide particles 316 may be in contactwith each other, the contact is random and an artifact of a mixing stepof a fabrication method for the antimicrobial material 300 a asdiscussed below. Therefore, contact between a portion of the grapheneparticles 314 and a portion of the metal oxide particles 316 is notintended, but may be present.

As shown in FIG. 40 , the graphene particles 314 and the metal oxideparticles 316 are present as graphene-metal oxide particle complexes314,316 that are uniformly dispersed throughout the polymeric matrix 312in the antimicrobial material 10 b. As such, the graphene particles 314carry the metal oxide particles 316 in the graphene-metal oxide particlecomplexes 314,316. Nonetheless, it is understood that there may be some,i.e., a minority portion, graphene particles 314 and/or metal oxideparticles 316 that are present in the polymeric matrix 312 individually,and not in a graphene-metal oxide particle complex 314,316. As discussedbelow, the graphene-metal oxide particle complexes 314,316 are formedprior to blending with the polymer that defines the polymeric matrix 312during a fabrication process.

In all of the descriptions of the current technology provided herein,the antiviral material 300 can alternatively be either the antiviralmaterial 300 a of FIG. 39 or the antiviral material 300 b of FIG. 40 ,unless otherwise stated. Moreover, the antimicrobial material 300 canalso include adjunct agents, such as plasticizers, compatibilizers,impact modifiers, light an UV stabilizers, heat stabilizers, colorpigments, fillers (e.g., glass fibers), talc, minerals, glass, physicalor chemical foaming agents, and combinations thereof.

The antimicrobial material 300 of FIG. 38 includes the polymer matrix312, i.e., the polymer, at a concentration of greater than or equal toabout 50 wt. % to less than or equal to about 99 wt. %. The grapheneparticles 314 have a concentration in the antimicrobial material 300 ofgreater than or equal to about 0.05 wt. % to less than or equal to about10 wt. %, greater than or equal to about 0.1 wt. % to less than or equalto about 5 wt. %, or greater than or equal to about 0.25 wt. % to lessthan or equal to about 1 wt. %, including at concentrations of about0.05 wt. %, about 0.1 wt. %, about 0.15 wt. %, about 0.2 wt. %, about0.25 wt. %, about 0.3 wt. %, about 0.35 wt. %, about 0.4 wt. %, about0.45 wt. %, about 0.5 wt. %, about 0.55 wt. %, about 0.6 wt. %, about0.65 wt. %, about 0.7 wt. %, about 0.75 wt. %, about 0.8 wt. %, about0.85 wt. %, about 0.9 wt. %, about 0.95 wt. %, about 1 wt. %, about 1.5wt. %, about 2 wt. %, about 2.5 wt. %, about 3 wt. %, about 3.5 wt. %,about 4 wt. %, about 4.5 wt. %, about 5 wt. %, about 5.5 wt. %, about 6wt. %, about 6.5 wt. %, about 7 wt. %, about 7.5 wt. %, about 8 wt. %,about 8.5 wt. %, about 9 wt. %, about 9.5 wt. %, or about 10 wt. %. Theadjunct agent (or plurality of adjunct agents) is present in theantimicrobial material 300 at a concentration of greater than or equalto about 0 wt. % to less than or equal to about 50 wt. %, such asgreater than or equal to about 0 wt. % to less than or equal to about 20wt. % talc, greater than or equal to about 0 wt. % to less than or equalto about 20 wt. % glass fiber, greater than or equal to about 0 wt. % toless than or equal to about 5 wt. % compatibilizer, and greater than orequal to about 0 wt. % to less than or equal to about 5 wt. % impactmodifier. The wt. % are based on the total weight of the antimicrobialmaterial 300.

The antimicrobial materials 300 a, 300 b of FIGS. 39 and 40 have thesame composition as the antimicrobial material 300, but further comprisegreater than or equal to 0 wt. % to less than or equal to about 20 wt. %of the metal oxide particles 316, individually, with the proviso that atleast one of the Cu₂O particles or the ZnO particles is present in theantiviral material 300 a, 300b. Therefore, the antiviral materials 300a, 300 b include greater than 0 wt. % to less than or equal to about 20wt. % of at least one of the Cu₂O particles or the ZnO particles. Thewt. % is based on the total weight of the antiviral material 300 a, 300b.

With reference to FIG. 41 , in some aspects the antimicrobial material300 is disposed over, about, and directly on a first sublayer orsubstrate 318. The first sublayer or substrate 318 can be a compressiblefoam, especially when the antimicrobial material 300 is soft andflexible, or a rigid substrate, especially when the antimicrobialmaterial 300 is rigid. Moreover, the first sublayer or substrate 18 canbe disposed on a second sublayer or substrate 320. For example, invarious aspects, the antiviral material 300 is a soft flexible material,such as a synthetic leather, that is disposed over a compressible foamfirst sublayer or substrate 318, which itself is disposed on a rigidsecond sublayer or substrate 320.

The antimicrobial materials 300, 300 a, 300 b described herein mayinclude at least the components described herein. However, it isunderstood that the antimicrobial materials 300, 300 a, 300 b mayalternatively be limited to the components described herein or to aportion of the components described herein. For example, theantimicrobial material 300 can include an antimicrobial agentcomprising, consisting essentially of, or consisting of graphene. By“consisting essentially of” it is meant that the antimicrobial material300 only intentionally includes graphene as the antimicrobial agent andis substantially free of any other antimicrobial agents. By“substantially free” it is meant that additional antimicrobial agentsmay be included in trace amounts, i.e., less than or equal to about 5wt. %, or less than or equal to about 1 wt. %, as impurities, whereinthe trace amounts do not affect the antimicrobial activity provided bythe graphene. Similarly, the antimicrobial materials 300 a, 300 b caninclude antimicrobial agents comprising, consisting essentially of, orconsisting of graphene and at least one of Cu₂O, ZnO, or AgO.

Methods of Fabricating Antimicrobial Materials and Articles

With reference to FIG. 42 , the current technology also provides amethod 350 of making an antimicrobial material, the antimicrobialmaterial being the antimicrobial materials 300, 300 a, 300 b discussedabove with reference to FIGS. 38-41 . At block 352, the method 350includes combining polymer particles including a polymer withantimicrobial particles. The antimicrobial particles include grapheneparticles when making the antimicrobial composition 30 of FIG. 38 . Whenmaking the antimicrobial composition 300 a of FIG. 39 , the method 350includes separately adding the graphene particles and the metal oxideparticles to the polymer particles. When making the composition 300 b ofFIG. 40 , the method 350 includes combining the graphene particles withmetal oxide particles and forming graphene particle-metal particlecomplexes, wherein the graphene particles carry the metal oxideparticles covalently or non-covalently. The graphene particle-metalparticle complexes are then added to the polymer particles during thecombining.

In block 354, the method 350 includes dry blending the antimicrobialparticles to form an antimicrobial powder or resin. The dry blending isperformed by mechanically mixing the polymer, additives, and theantimicrobial particles at high speeds. The high speed mixing creates ahigh shear environment that increases temperature and promotesabsorption. As can be seen in block 356, the method 350 can then includecreating a molded product from the antimicrobial powder by slushmolding.

In block 358, the method 350 includes melt compounding the polymerparticles with the graphene particles to form a melt and extruding themelt to form an extruded material including the graphene particles, andoptionally the metal oxide particles, dispersed in the polymer. The meltcompounding and extruding is performed, for example, with a twin-screwextruder. The extruded material can be a solid, unitary thread or it canhave a hollow interior, such as a cylinder or pipe.

In block 360, the method 350 includes processing the extruded materialby calendaring or casting to form rolled goods or cast films as theantimicrobial material. In block 362, the method includes creating amolded product from the antimicrobial material by cutting and sewing,and thermoforming, wherein the thermoforming can be vacuum forming,pressure forming, or twin sheet forming.

In block 364, the method 350 includes pelletizing the extruded materialto form antimicrobial pellets including the graphene particles, andoptionally the metal oxide particles, dispersed in a polymeric pellet.The pelletizing is performed by cutting or grinding the extrudedmaterial into the antimicrobial pellets. The antimicrobial pellets canthen be subjected to various processing methods. For example, a firstprocessing method beginning in block 366 and includes creating a moldedproduct by injection molding with the antimicrobial pellets. Methods ofinjection molding are known in the art. A second processing methodbegins in block 368 and includes grinding the antimicrobial pellets toform a slush powder. In block 370 the method 350 then includes creatinga molded product by subjecting the slush powder to slush molding. Athird processing method begins in block 372 and includes processing theantimicrobial pellets by extruding, calendaring, or casting to createrolled goods or cast films as the antimicrobial material. The rolledgoods or cast films can be processed by cutting and sewing and/or bythermoforming as discussed above.

When the antimicrobial material is a flexible and soft, such as when theantimicrobial material is a synthetic leather, as a non-limitingexample, the method may also include disposing the antimicrobial filmabout a compressible foam substrate.

Methods for creating molding products depend on polymer type and anintended application. Slush molding requires desired particle sizes,whereas injection molding requires desired melt flow (as determined by amelt flow index (MFI)). Plasticized PVC with antimicrobial properties ofthe current technology are prepared using a dry blending/alloyingtechnique, whereas antimicrobial TPU/TPO soft skin materials areprepared using twin-screw extrusion with defined screw profile followedby hydrogrinding to achieve desired particle size and bulk density. Theend-product from these materials (e.g., PVC, TPU, and TPO) can be madeusing slush molding or thermoforming techniques.

A calendaring and/or cast film process is used to produce rolledgoods/cast films/calendared rolls and these products are used for wrapup applications in automotive and aircraft interiors, furnishings,electronic housings, office furniture, and the like. The process ofproducing calendared goods begins with obtaining pellets from a primaryprocess of extrusion compounding, i.e., plasticized PVC, TPU, TPO, PE,PP (or other polymers) are mixed with antimicrobial additives (e.g.,graphene, graphene derivatives, metal oxides) in twin-screw extrusion toobtain pellets or calendared directly to form rolls/cast films. Ifpellets are obtained in extrusion process, they are fed intocalendaring/cast film extruder to obtain rolled goods. The calendaredgoods/sheets are used, for example, in thermoforming or vacforming(thermoforming with vacuum) to produce a desired shape and application.

Cu₂O is the source of Cu¹⁺ions, ZnO is the source of Zn²⁺, and AgO isthe source of Ag¹⁺, which act as antimicrobials agent against H1N1,human corona viruses (including SARS-CoV-1 and SARS-CoV-2), anddifferent species of bacteria and fungi. In regard to Cu₂O, the copperis not fully oxidized and remains active and very unstable. Thisinstability allows the copper to remain highly reactive, which can leadto the formation of free radicles that can denature RNA and/or DNA cellswithin viruses with or without viral envelopes. The inactivation methodis mediated by direct contact of copper on surfaces antimicrobialmaterials of the current technology. Graphene is used as anantimicrobial agent and for immobilizing the antimicrobial ions derivedfrom the metal oxides, and increases the effectiveness of theantimicrobial materials against target viruses. The graphene can have6-10 layers, which are exfoliated into single, double, and/or triplelayers during twin extrusion with specially designed screws forimproving dispersive and distributive mixing.

In one example, the antimicrobial material is a TPU skin material having80-95 wt. % TPU resin, and 1-20 wt. % Cu₂O immobilized in 0.05-10 wt. %graphene. Raw graphene powder used to make the TPU skin material canhave a maximum of 10 layers. In another example, dry blendedantimicrobial PVC includes 80-95 wt. % of plasticized PVC resin, and1-20 wt. % of Cu₂O, immobilized in 0.05-10 wt. % graphene. Raw graphenepowder used to make the dry blended antimicrobial PVC can have a maximumof 10 layers. In yet another example, an antimicrobial TPO skin materialhas 80-95 wt. % of TPO resin, and 1-20 wt. % of Cu₂O immobilized in0.05-10 wt. % graphene. An exemplary antimicrobial class-A materials(including, e.g., PP, TPO, and/or TPE) includes 70-95 wt. % of TPOresin, 5-20 wt. % talc, and 1-10 wt. percent of Cu₂O, immobilized in0.05-10 wt. % graphene.

As discussed above, ZnO also has antimicrobial activity. There are anumber of mechanisms by which Zn interferes with viral replicationcycles. These mechanisms include free virus inactivation, inhibition ofviral uncoating, viral genome transcription, and viral proteintranslation and polyprotein processing.

An example of an antiviral class-A material (including, e.g., PP, TPO,and/or TPE) includes 70-95 wt. % TPO resin, 5-20 wt. % talc, and 1-10wt. % of ZnO. In another example, an antimicrobial TPU skin material has80-95 wt. % of TPU resin, and 1-20 wt. % of zinc oxide immobilized in0.05-10 wt. % graphene. Raw graphene powder used to make theantimicrobial TPU skin material can have a maximum of 10 layers. In yetanother example, dry blended antimicrobial PVC includes 80-95 wt. % ofplasticized PVC resin, and 1-20 wt. % of ZnO, immobilized in 0.05-10 wt.% graphene. Raw graphene powder used to make the dry blendedantimicrobial PVC can have a maximum of 10 layers. An exemplaryantimicrobial TPO skin material has 80-95 wt. % of TPO resin, and 1-20wt. % of ZnO immobilized in 0.05-10 wt. % graphene

The antiviral activity of the antimicrobial materials can be determinedby exposure to SARS-Covid-2 for, e.g., about 15 minutes, about 30minutes, about 45 minutes, about 1 hour, about 6 hours, about 12 hours,and about 24 hours, similar to what is provided by ISO 21702.

Embodiments of the present technology are further illustrated throughthe following non-limited example.

EXAMPLE

Table 1 provides exemplary antimicrobial soft skin materials inaccordance with various aspects of the current technology. Theantimicrobial soft skin materials are prepared by adding all solidcomponents into a Henschel mixer and mixing on low speed for 3 minutesfor pre-heating purposes. After 3 minutes, 70% of polyol esterplasticizer is added into the mixer with stirring at low speed. Thespeed of the mixer is increased and material is mixed until atemperature of about 190° F. is reached. At 190° F., a remaining 30% ofpolyol ester plasticizer is added along with heat and light stabilizerswith low speed mixing. A second plasticizer can also be added at thistime. The mixer is then turned to high speed and mixed until it reachesa minimum temperature of 235° F. The material is then cooled to 120° F.where the drying agent is then added and an additional cooling period toabout 105° F. allows for the addition of filler.

TABLE 1 Exemplary PVC-based antimicrobial soft skin materials. DryBlends Parts by mass (PVC Formulations) 1 2 PVC suspension resin 100 100Polyol Ester Plasticizer  40-100  75-100 Adipate Ester Plasticizer  0 10 to 40 Heat Stabilizer  0.4 to 4  0.4 to 4 Light Stabilizer  0.4 to 1 0.4 to 1 Epoxidized soy bean oil  1 to 10  5 to 15 PVC dispersion resin 1 to 10  1 to 10 Filler (CaCo3, Talc, etc.)  1 to 10  1 to 10 Graphene 0 to 10  0 to 10 Cuprous Oxide  0 to 15  0 to 15 Zinc Oxide  0 to 10  0to 10 Graphene-Cuprous Oxide complex  0 to 10  0 to 10

Table 2 provides exemplary antimicrobial soft skin materials inaccordance with various aspects of the current technology. Theantimicrobial soft skin materials are prepared by feeding graphene, TPUor TPO, and/or metal oxides into twin-screw extruder for melt blendingfollowed by grinding to obtain a slush grade powder. Optional additives,such as light and UV stabilizers, compatibilizers, color pigments, andthe like, may also be added. This formulation creates a high performanceTPU or TPO with antiviral properties.

TABLE 2 Exemplary TPU- or TPO-based antimicrobial soft skin materials.Melt Blended Formulations Weight Percent (TPU & TPO) 3 4 ThermoplasticPolyurethane (TPU) 80 to 95  0 Thermoplastic Polyolefin(TPO)/Olefin-Block Copolymer (OBC)  0 65 to 75 Heat Stabilizer  1 to 5 1 to 5 Light Stabilizer  1 to 5  1 to 5 Compatibilizer  0 to 5  0 to 5Graphene  0 to 10  0 to 10 Cuprous Oxide  0 to 15  0 to 15 Zinc Oxide  0to 10  0 to 10 Graphene-Cuprous Oxide Complex  0 to 10  0 to 10

Table 3 provides exemplary hard antimicrobial materials in accordancewith various aspects of the current technology. The hard antimicrobialmaterials are prepared by feeding graphene, TPU and/or metal oxides intoa twin-screw extruder for melt blending followed by grinding to obtainslush grade powder. Optional additives such as light and UV stabilizers,compatibilizers, color pigments, and the like may also be added. Thisformulation creates a high performance PP, TPO, ABS, PC, and PVC withantiviral properties.

TABLE 3 Exemplary PP-, TPO-, ABS-, PC-, and PVC-based hard antimicrobialmaterials. Weight Percent 5 6 7 8 9 Polypropylene (PP) 65 to 95  0  0  0 0 Thermoplastic Polyolefin (TPO)/Olefin  0 65 to 95  0  0  0 BlockCopolymer/Styrene-ethylene-butylene- styrene Acrylonitrile butadienestyrene (ABS)  0  0 65 to 95  0 to 20  0 Polycarbonate (PC)  0  0  0 65to 95  0 Polyvinyl Chloride (PVC)  0  0  0  0 to 20 65 to 95Compatibilizer  0 to 5  0 to 5  0 to 5  0 to 5  0 to 5 Talc  0 to 20  0to 20  0 to 20  0 to 20  0 to 20 Glass/Carbon Fiber  0 to 20  0 to 20  0to 20  0 to 20  0 to 20 Graphene  0 to 10  0 to 10  0 to 10  0 to 10  0to 30 Cuprous Oxide  0 to 15  0 to 15  0 to 15  0 to 15  0 to 15 ZincOxide  0 to 10  0 to 10  0 to 10  0 to 10  0 to 10 Graphene-CuprousOxide Complex  0 to 10  0 to 10  0 to 10  0 to 10  0 to 10

Process for producing graphene-metal oxide complexes. Graphene-metaloxide complexes were prepared using a mechanical blending method. Cu₂Oand ZnO have respective particle sizes of about 100 μm and about 50 μm.Graphene black was separately uniformly mixed with Cu₂O and ZnO inalcohol at weight ratios of about 1:10. Graphene/Cu₂O and graphene/ZnOcomplexes were obtained following stirring for 6 h and drying in an ovenat below 60° C. for 3 h.

Test material preparation. The CpK antiviral materials were provided astwo material types. Type 1 was a soft pliable plastic material whileType 2 was a hard-plastic disk. In preparation for testing, the top andbottom of the CpK antiviral materials within sterile biosafety cabinet(BSC) were disinfected with 70% EtOH with a 5 min contact time. Aftersterilization, the materials were stored in sterile 100 mm polystyrenedishes. All of the materials were cut into −0.5×0.5 cm squares andplaced into sterile 1.5 ml tubes.

SARS-CoV-2 preparation and CpK Treatment. The SARS-CoV-2 virus stock ata titer of 105.8 infectious units (IU)/ml was diluted to 102.9 (IU)/ml.A volume of 850 μl of the diluted viral stock was added to a 1.5 ml tubecontaining the square of CpK antiviral material. The tube containing thevirus and CpK antiviral material was placed on a tube rotator for 24 hrsat 220° C. with 100 μl samples collected at 1 hr, 3 hr, 6 hr, 12 hr, and24 hrs. Viral supernatants from these time points were cultured in astandard TCID50 experiment to measure reduction in viral titer. As apositive control, virus was added at the same concentration to the 1.5ml tubes for 1 to 24 hrs. As a negative control and to determinematerial toxicity, media containing no virus was added to each of thematerials for 1 to 24 hrs. Collected supernatants were diluted 100-foldto dilute any chemicals/materials that may have been released from theCpK antiviral material during incubation. The collected supernatantswere further 100-fold diluted serially from 1:100 to 1:100000 and thenadded to 20,000 Vero E6 cells in 96 well flat bottom plates. The 1:100dilution of the virus stock infecting 20,000 cells represents an MOI of0.5. Infection of the Vero E6 cells was monitored by viral cytotoxicity.Cell toxicity of the supernatants derived material in the absence ofvirus (diluted 1:100) was measured visually. Results are shown in Table4.

TABLE 4 Results of antiviral testing. Reduction Factor Time Viral(Log10) % Viral Material Name (hr) Titer v. Control Reduction  1 0 >699.9%  3 0 >6 99.9% TPU-Graphene-Cu2O  6 0 >6 99.9% (Soft Plastic) 120 >6 99.9% 24 0 >6 99.9%  1 10{circumflex over ( )}2.8   0  0  3 0 >699.9% TPU-Graphene  6 0 >6 99.9% (Soft Plastic) 12 0 >6 99.9% 24 0 >699.9% CLB5  1 10{circumflex over ( )}2.8   0  0  3 0 >6 99.9% PVC-Cu2O 6 0 >6 99.9% (Soft Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  110{circumflex over ( )}2.8   0  0  3 0 >6 99.9% PVC-ZnO  6 0 >6 99.9%(Soft Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  1 10{circumflex over ( )}2.8  0  0  3 10{circumflex over ( )}2.8   0  0 PVC-Graphene-  6 0 >6 99.9%Cu2OComplex (Soft Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  1 10{circumflexover ( )}2.8   0  0  3 10{circumflex over ( )}2.8   0  0 PVC-CU2010  60 >6 99.9% (Soft Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  1 10{circumflexover ( )}2.8   0  0  3 10{circumflex over ( )}2.8   0  0 TPO-Cu2O  60 >6 99.9% (Hard Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  1 1012 2.8   0  0 3 10{circumflex over ( )}2.8   0  0 TPO-Cu2O  6 10{circumflex over( )}2.8   0  0 (Soft Plastic) 12 0 >6 99.9% 24 0 >6 99.9%  110{circumflex over ( )}2.8   0  0  3 10{circumflex over ( )}2.8   0  0TPU-Graphene-Cu2O  6 10{circumflex over ( )}2.8   0  0 (Soft Plastic) 120 >6 99.9% 24 0 >6 99.9%

The foregoing description of the embodiments has been provided forpurposes of illustration and description. It is not intended to beexhaustive or to limit the disclosure. Individual elements or featuresof a particular embodiment are generally not limited to that particularembodiment, but, where applicable, are interchangeable and can be usedin a selected embodiment, even if not specifically shown or described.The same may also be varied in many ways. Such variations are not to beregarded as a departure from the disclosure, and all such modificationsare intended to be included within the scope of the disclosure.

What is claimed is:
 1. An antiviral material comprising: a polymericmatrix; and graphene particles dispersed in the polymeric matrix at aconcentration of greater than or equal to about 0.05 wt. % to less thanor equal to about 10 wt. % based on the total weight of the antiviralmaterial, wherein the antiviral material comprising the grapheneparticles exhibits antiviral activity; wherein the graphene particleshave greater than or equal to 6 to less than or equal to 10 layers,wherein each layer comprises carbon atoms arranged in a two-dimensionallattice; wherein the antiviral material inactivates than or equal toabout 99% of viral particles in contact with the antiviral material inless than or equal to about 1 hour.
 2. The antiviral material accordingto claim 1, comprising: greater than or equal to about 90 wt. % to lessthan or equal to about 99 wt. % of the polymeric matrix; and greaterthan or equal to about 0.05 wt. % to less than or equal to about 0.5 wt.% of the graphene particles or greater than or equal to about 4.5 wt. %to less than or equal to about 10 wt. % of the graphene particles,wherein the wt. % is based on the total weight of the antiviralmaterial.
 3. The antiviral material according to claim 1, wherein theantiviral material is flexible and the polymeric matrix includes apolymer comprising polyvinyl chloride (PVC), a thermoplastic elastomer(TPE), or a combination thereof.
 4. The antiviral material according toclaim 3, wherein the TPE comprises a thermoplastic polyurethane (TPU), athermoplastic polyolefin (TPO), thermoplastic vulcanizates (TPV), orcombinations thereof.
 5. The antiviral material according to claim 3,wherein the antiviral material comprises a layer comprising thepolymeric matrix and a foam layer, wherein the layer comprises thepolymeric matrix is disposed on the foam layer.
 6. The antiviralmaterial according to claim 1, wherein the antiviral material is rigidand the polymeric matrix includes a polymer comprising polyvinylchloride (PVC), polypropylene (PP), acrylonitrile butadiene styrene(ABS), polycarbonate (PC), PC/ABS, PC/PP, a thermoplastic elastomer(TPE), or combinations thereof.
 7. The antiviral material according toclaim 1, further comprising: metal oxide particles dispersed in thepolymer matrix, the metal oxide particles comprising at least one ofcuprous oxide (Cu₂O) particles or zinc oxide (ZnO) particles.
 8. Theantiviral material according to claim 7, comprising: greater than orequal to about 50 wt. % to less than or equal to about 98 wt. % of thepolymer; greater than or equal to about 0.05 wt. % to less than or equalto about 10 wt. % of the graphene particles; greater than or equal toabout 0 wt. % to less than or equal to about 20 wt. % of the Cu₂Oparticles; and greater than or equal to about 0 wt. % to less than orequal to about 20 wt. % of the ZnO particles, with the proviso that atleast one of the Cu₂O particles or the ZnO particles is present in theantiviral material.
 9. The antiviral material according to claim 1,wherein the antiviral material inactivates greater than or equal toabout 99% of viral particles in contact with the antiviral material inless than or equal to about 1 hour and maintains the viral inactivationfor at least 24 hours.
 10. The antiviral material according to claim 1,further comprising a vehicular interior panel including the polymericmatrix and graphene particles, the panel further comprising a flexiblefastener.
 11. An automotive vehicle instrument panel having a surfacecomprising the antiviral material according to claim
 1. 12. A seathaving a surface comprising the antiviral material according to claim 1.13. An electrical device comprising an exterior surface having theantiviral material according to claim
 1. 14. An automotive vehicleinterior panel comprising: a flexible exterior surface comprising anantiviral material, wherein the antiviral material is powder and theflexible exterior surface is formed by molding with the powder; a rigidsubstrate; and a compressible foam disposed between the flexibleexterior surface and the rigid substrate, wherein the antiviral materialcomprises a polymeric matrix, and graphene particles dispersed withinthe polymeric matrix at a concentration of greater than or equal toabout 0.05 wt. % to less than or equal to about 10 wt. % based on thetotal weight of the antiviral material, and wherein the antiviralmaterial exhibits antiviral activity including viral inactivation ofgreater than or equal to about 50% of viral particles in contact withthe antiviral material in less than or equal to about 1 hour; whereinthe graphene particles have at least 2 layers, wherein each layercomprises carbon atoms arranged in a two-dimensional lattice.
 15. Theautomotive vehicle interior panel according to claim 14, wherein theantiviral material further comprises at least one of cuprous oxide(Cu₂O) particles or zinc oxide (ZnO) particles.
 16. The automotivevehicle interior panel according to claim 15, wherein the at least oneof Cu₂O particles or ZnO particles are coupled to the graphene in agraphene-metal oxide particle complex.
 17. The automotive vehicleinterior panel according to claim 14, wherein the interior panel isformed at least in part by molding with a slush molding and is anA-pillar, a B-pillar, a C-pillar, an instrument panel, a steering wheelskin, an airbag cover, a door trim panel, a center console, a kneebolster, a seat mechanism cover, or a sun visor.
 18. A vehicle class-Ainterior surface comprising an antiviral material comprising: apolymeric matrix; and graphene particles dispersed in the polymericmatrix at a concentration of greater than or equal to about 0.05 wt. %to less than or equal to about 10 wt. % based on the total weight of andto form the antiviral material, wherein the antiviral material exhibitsantiviral activity on the vehicle class-A interior surface including theviral inactivation of greater than equal to about 50% of viral particlesin contact with the antiviral material in less than or equal to about 1hour; wherein the graphene particles have greater than or equal to 2 toless than or equal to 10 layers.
 19. The vehicle class-A interiorsurface according to claim 18, further comprising: metal oxide particlesdispersed in the polymeric matrix.
 20. The vehicle class-A interiorsurface according to claim 19, wherein the metal oxide particlescomprise cuprous oxide (Cu₂O) particles, zinc oxide (ZnO) particles, ora combination thereof.
 21. The vehicle class-A interior surfaceaccording to claim 18, being a vehicle occupant-accessible surfacecovering an inner rigid substrate of an A-pillar, a B-pillar, aC-pillar, an instrument panel, a steering wheel, an airbag cover, a doortrim panel, a door handle, a pillar handle, a roof handle, a centerconsole, a knee bolster, a seat mechanism cover, or a sun visor.
 22. Anautomotive vehicle instrument panel comprising: a flexible exteriorsurface comprising an antiviral material; a rigid substrate; and acompressible foam disposed between the flexible exterior surface and therigid substrate, wherein the antiviral material comprises a polymericmatrix, and graphene particles dispersed within the polymeric matrix ata concentration of greater than or equal to about 0.05 wt. % to lessthan or equal to about 10 wt. % based on the total weight of theantiviral material, and wherein the antiviral material exhibitsantimicrobial activity on the automotive vehicle instrument panelincluding viral inactivation of greater than or equal to about 50% ofviral particles in contact with the antiviral material in less than orequal to about 1 hour; wherein the graphene particles have greater thanor equal to 2 to less than or equal to 10 layers.
 23. The instrumentpanel according to claim 22, wherein the antiviral material furthercomprises metal oxide particles dispersed in the polymeric matrix. 24.The instrument panel according to claim 23, wherein the metal oxideparticles comprise cuprous oxide (Cu₂O) particles, zinc oxide (ZnO)particles, or a combination thereof.
 25. The instrument panel accordingto claim 23, wherein the graphene particles carry the metal oxideparticles.
 26. The instrument panel according to claim 23, whereingraphene particles and the metal oxide particles are independentlydispersed within the polymeric matrix.
 27. The instrument panelaccording to claim 22, wherein the polymeric matrix comprises polyvinylchloride (PVC), a thermoplastic elastomer (TPE), or a combinationthereof.
 28. The instrument panel according to claim 22, furthercomprising an airbag cover comprising a frangible seam on a backsidesurface of the flexible exterior surface.
 29. The antiviral materialaccording to claim 1, wherein the graphene particles have a diameter ofgreater than or equal to about 750 nm to less than or equal to about 250μm, greater than or equal to about 1 μm to less than or equal to about100 μm, or greater than or equal to about 1 μm to less than or equal toabout 50 μm.